We present the novel potential application of imine-based covalent organic frameworks (COFs), formed by the direct Schiff reaction between 1,3,5-tris(4-aminophenyl)benzene and ...1,3,5-benzenetricarbaldehyde building blocks in m-cresol or acetic acid, named RT-COF-1 or RT-COF-1Ac/RT-COF-1AcB. The post-synthetic treatment of RT-COF-1 with LiCl leads to the formation of LiCl@RT-COF-1. The ionic conductivity of this series of polyimine COFs has been characterized at variable temperature and humidity, using electrochemical impedance spectroscopy. LiCl@RT-COF-1 exhibits a conductivity value of 6.45 × 10–3 S cm–1 (at 313 K and 100% relative humidity) which is among the highest values so far reported in proton conduction for COFs. The mechanism of conduction has been determined using 1H and 7Li solid-state nuclear magnetic resonance spectroscopy. Interestingly, these materials, in the presence of controlled amounts of acetic acid and under pressure, show a remarkable processability that gives rise to quasi-transparent and flexible films showing in-plane structural order as confirmed by X-ray crystallography. Finally, we prove that these films are useful for the construction of proton exchange membrane fuel cells (PEMFC) reaching values up to 12.95 mW cm–2 and 53.1 mA cm–2 for maximum power and current density at 323 K, respectively.
Schiff-condensation reactions carried out between 1,6-diaminopyrene (DAP) and the tritopical 1,3,5 benzenetricarbaldehyde (BTCA) or 2,4,6-triformylphloroglucinol (TP) ligands give rise to the ...formation of two-dimensional imine-based covalent-organic frameworks (COFs), named IMDEA-COF-1 and -2, respectively. These materials show dramatic layer-packing-driven fluorescence in solid state arising from the three-dimensional arrangement of the pyrene units among layers. Layer stacking within these 2D-COF materials to give either eclipsed or staggered conformations can be controlled, at an atomic level through chemical design of the building blocks used in their synthesis. Theoretical calculations have been used to rationalize the different preferential packing between both COFs. IMDEA-COF-1 shows green emission with absolute photoluminescence quantum yield of 3.5% in solid state. This material represents the first example of imine-linked 2D-COF showing emission in solid state.
Better and more efficient membranes are needed to face imminent and future scientific, technological and societal challenges. New materials endowed with enhanced properties are required for the ...preparation of such membranes. Metal and Covalent Organic Frameworks (MOFs and COFs) are a new class of crystalline porous materials with large surface area, tuneable pore size, structure, and functionality, making them a perfect candidate for membrane applications. In recent years an enormous number of articles have been published on the use of MOFs and COFs in preparation of membranes for various applications. This review gathers the work reported on the synthesis and preparation of membranes containing MOFs and COFs in the last 10 years. Here we give an overview on membranes and their use in separation technology, discussing the essential factors in their synthesis as well as their limitations. A full detailed summary of the preparation and characterization methods used for MOF and COF membranes is given. Finally, applications of these membranes in gas and liquid separation as well as fuel cells are discussed. This review is aimed at both experts in the field and newcomers, including students at both undergraduate and postgraduate levels, who would like to learn about preparation of membranes from crystalline porous materials.
The current technology of air‐filtration materials for protection against highly toxic chemicals, that is, chemical‐warfare agents, is mainly based on the broad and effective adsorptive properties of ...hydrophobic activated carbons. However, adsorption does not prevent these materials from behaving as secondary emitters once they are contaminated. Thus, the development of efficient self‐cleaning filters is of high interest. Herein, we report how we can take advantage of the improved phosphotriesterase catalytic activity of lithium alkoxide doped zirconium(IV) metal–organic framework (MOF) materials to develop advanced self‐detoxifying adsorbents of chemical‐warfare agents containing hydrolysable PF, PO, and CCl bonds. Moreover, we also show that it is possible to integrate these materials onto textiles, thereby combining air‐permeation properties of the textiles with the self‐detoxifying properties of the MOF material.
The silk of human kindness: Insertion of lithium alkoxides in zirconium metal–organic frameworks (MOF) which are then deposited on silk fibers gives rise to protective fabrics capable of self‐detoxifying chemical‐warfare agents. The fabrics combine the air‐permeation properties of the textiles with the highly active phosphotriesterase catalytic activity of the MOF for the hydrolysis of PF, PO, and CCl bonds.
Two isoreticular series of pyrazolate-based 3D open metal–organic frameworks, MBDP_X, adopting the NiBDP and ZnBDP structure types H2BDP = 1,4-bis(1H-pyrazol-4-yl)benzene, were synthesized with the ...new tagged organic linkers H 2 BDP_X (X = −NO2, −NH2, −OH). All of the MBDP_X materials have been characterized through a combination of techniques. IR spectroscopy proved the effective presence of tags, while X-ray powder diffraction (XRPD) witnessed their isoreticular nature. Simultaneous TG/DSC analyses (STA) demonstrated their remarkable thermal stability, while variable-temperature XRPD experiments highlighted their high degree of flexibility related to guest-induced fit processes of the solvent molecules included in the channels. A structural isomer of the parent NiBDP was obtained with a sulfonate tagged ligand, H 2 BDP_SO 3 H. Structure solution from powder diffraction data collected at three different temperatures (room temperature, 90, and 250 °C) allowed the determination of its structure and the comprehension of its solvent-related flexible behavior. Finally, the potential application of the tagged MOFs in selective adsorption processes for gas separation and purification purposes was investigated by conventional single component adsorption isotherms, as well as by advanced experiments of pulse gas chromatography and breakthrough curve measurements. Noteworthy, the results show that functionalization does not improve the adsorption selectivity (partition coefficients) for the resolution of gas mixtures characterized by similar high quadrupole moments (e.g., CO2/C2H2); however, the resolution of gas mixtures containing molecules with highly differentiated polarities (i.e., N2/CO2 or CH4/CO2) is highly improved.
Tunable hydrophobicity: Efficient air filters for the protection against chemical warfare agents might be achieved by surface functionalization of the pores in robust metal–organic frameworks (MOFs) ...with fluoroalkyl residues and the precise control of their pore size (see picture). These MOFs capture harmful volatile organic compounds even under extremely moist conditions (80 % relative humidity).
The ionic conductivity properties of the face‐centered cubic Ni8(OH)4(H2O)2(BDP_X)6 (H2BDP_X=1,4‐bis(pyrazol‐4‐yl)benzene‐4‐X with X=H (1), OH (2), NH2 (3)) metal–organic framework (MOF) systems as ...well as their post‐synthetically modified materials KNi8(OH)5(EtO)(BDP_X)5.5 (1@KOH, 3@KOH) and K3Ni8(OH)3(EtO)(BDP_O)5 (2@KOH), which contain missing‐linker defects, have been studied by variable temperature AC impedance spectroscopy. It should be noted that these modified materials exhibit up to four orders of magnitude increase in conductivity ‐values in comparison to pristine 1–3 systems. As an example, the conductivity value of 5.86×10−9 S cm−1 (activation energy Ea of 0.60 eV) for 2 at 313 K and 22 % relative humidity (RH) increases up to 2.75×10−5 S cm−1 (Ea of 0.40 eV) for 2@KOH. Moreover, a further increase of conductivity values up to 1.16×10−2 S cm−1 and diminution of Ea down to 0.20 eV is achieved at 100 % RH for 2@KOH. The increased porosity, basicity and hydrophilicity of the 1@KOH–3@KOH materials compared to the pristine 1–3 systems should explain the better performance of the KOH‐modified materials.
The missing link: The deliberate introduction of defects on fcu frameworks by KOH/EtOH, leading to missing‐linker defects and metal cluster basification, is responsible for a boosting of the ion conductivity and depletion of activation energy.
Metal Organic Frameworks (MOFs) present high surface areas, various pore topology as well as good stabilities. The functionalities and porosity can be tuned by using different linkers with various ...functional groups and a wide range of linker lengths. These properties make them good candidates in membrane separation applications. In this work, we propose a simple UiO-66 MOF-based membrane fabrication method following two steps. First, the α-alumina tubular membrane support was dip-coated with MOF-polymer hybrid nanoparticles (NPs). These NPs were prepared via one-pot synthesis by adding poly (methacrylic acid)-
-poly (methyl methacrylate) (PMAA-
-PMMA) NPs to the classical acetic acid-modulated UiO-66 or UiO-66-NH
synthesis formulation. Second, secondary membrane growth was applied to give rise to a continuous and homogeneous crystalline MOF membrane layer. The gas permeances (He, N
, CO
and SF
) tests confirmed high membrane permeability with no macro-defects. The as-prepared membranes that were used for dye separation (Rhodamine B) showed relatively good separation capacity.
Global population growth and water resource scarcity are significant social problems currently being studied by many researchers focusing on finding new materials for water treatment. The aim is to ...obtain quality water suitable for drinking and industrial consumption. In this sense, an emergent class of crystalline porous materials known as Covalent-Organic Frameworks (COFs) offers a wide range of possibilities since their structures can be designed on demand for specific applications. Indeed, in the last decade, many efforts have been made for their use in water treatment. This perspective article aims to overview the state-of-the-art COFs collecting the most recent results in the field for water detection of pollutants and water treatment. After the introduction, where we overview the classical design strategies on COF design and synthesis for obtaining chemically stable COFs, we summarize the different experimental methodologies used for COFs processing in the form of supported and free-standing membranes and colloids. Finally, we describe the use of COFs in processes involving the detection of pollutants in water and wastewater treatment, such as the capture of organic compounds, heavy metals, and dyes, the degradation of organic pollutants, as well as in desalination processes. Finally, we provide a perspective on the field and the potential technological use of these novel materials.
To review the cases of atypical squamous cells (ASC), cannot exclude squamous intraepithelial lesion (ASC-H) diagnosed at a single institution and to discuss the interpretation challenges and ...clinical management of these cases.
The ASC-H cases diagnosed at our institution from 2006 to 2015 were studied retrospectively; of 159,000 Pap smears, there were 959 cases of ASC of undetermined significance (ASC-US) and 148 cases of ASC-H. We have reviewed the clinical records of the ASC-H cases, and data have been analyzed using SPSS 20.0.
Median age was 43.1 years; 49.6% of the patients had previous cervical cytologies, and 55.9% of them were negative. Following ASC-H diagnosis, another smear was obtained in 97.1% of the cases and in 67.6% a biopsy was performed. Biopsy revealed low-grade dysplasia in 18.8% of the cases, high-grade dysplasia in 27.8%, and infiltrating carcinoma in 2.3%. Patients with significant lesions in histology were younger than patients with negative results (p = 0.08). A diagnosis of ASC-H/squamous intraepithelial lesion in the repeated cytology had a sensitivity of 74.2%, specificity of 39.6%, positive predictive value of 44.8%, and negative predictive value of 70% for the diagnosis of dysplasia.
ASC-H diagnosis is associated with a high incidence of histological high-grade lesions. A repeat cytology can aid in the selection of high-risk patients, but there may be false-negative results.
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